A CLASSIFICATION

OF THE

2:1 CLAY

MINERALS

Cnanr,Bs Enwano Weavnn,* The Pennsylaania State College,

State College,P ennsylvania.
Ansrnact
in whichthe per centof the total
A classification
of the 2: 1 claymineralsis presented
replacement which occurs in the octahedral and tetrahedral sheets is considered to be of
primary importance. The secondary division is based upon the degree of expansion and the
nature of the external cations.

INrnonuctroN
During a study of the potassium bentonites from the Ordovician limestones of Pennsylvania (Weaver and Bates, 1951) additional evidence
was found indicating that the difierencesbetween illite and montmorillonite are not as great as is commonly supposed.Bradley (1944) found
that many of the illite-like clays such as glimmerton, bravaisite, Grundy
illite, metabentonite, and some glauconites contain expanded layers.
Nagelschmidt (1944) found that when illite is treated with CaCl2, portions of the non-expanded layers expand. White (1950) has shown that
by treating illite with MgCl2 and precipitating the exchangedpotassium
the illite expands and gives a montmorillonite r-ray pattern. It is thought
that many of the montmorillonite minerals, particularly beidellite, contain some non-expanded layers which are indicated by the presenceof
potassium in the chemical analyses. Caillbre and H6nin (1949) have
shown that by boiling montmorillonite in KOH the 001 spacing shifts
to the 10 A value characteristic of illite. Barshad (1948) has shown that
biotite will exchange K for Mg and form an expanded Iattice with a
value greater than 10 A. Many soils scientists have shown that K can
be "fixed" by montmorillonite and recently Mortland and Gieseking
(1951) causedboth montmorillonite and hectorite to collapseto 10 A by
placing them in a solution of KzSiOaand drying at 110oC. Kunze (1952)
was able to collapseseveral 14 A soil vermiculites to 10 A by drying them
from a solution of K C:HrOz.
These findings suggestthat the same fundamental 211 layers can form
either an expanded or a non-expanded clay and that it is relatively easy
to change the state of expansion. ft is proposed that the existenceof an
expanded or a non-expanded lattice is dependent upon the cations in
interlayer positions rather than upon the composition of the 2:I layers
in the lattice and that the type of cation present is independent of the
composition of the layers.
The ideas formulated above are illustrated by the illite-montmorillonite groups of minerals and are further supported by studies of
K-bentonites.
* Shell Development
Houston 25, Texas.

Company, Exploration

698

and Production Research Laboratory,

A CLASSIFICATION OF TEE 2:I CLAV MINERALS

699

Irr-rrB Vnnsus MoNruonrlLoNITE

General

criteria referred to are as follows:

with a c.1. Illite, as usually defined, has a non-expanded lattice,
to 30 A
12
Iattice,
expanded
an
spacing of 10 A. Montmorillonite has
in the direction of the c axis.
in differ2. Illite commonly gives a hydroxyl-endothermal reaction
montmorillonite
the
whereas
ential thermal analysis-curves at 500-600,
reaction usually occurs at 600-750' C.
structural
3. Except for the external cations K, Na, Mg, and Ca' the
cases
many
in
and
similar,
are
formulas of ittit"t and montmorillonites
characteristic
is
cation
external
identical. The predominance of K as an
of illite.
X-ray Dota
of identifying
Probably the most widely used and most reliable means
When a
diffraction'
r-ray
is
by
groups
the minerals of these two clay
is
considered
clay
the
obtained
is
io-A .r*tu" for the first 001 rpu.i"g
has a value of
to be non_expandedand is caied illite. If the r-ray line
lattice and
expanded
an
have
to
gr"ut"r, the clay is considered
12 i.,
chlorite).
or
vermiculite
not
is
is called montmorillonite (assuming it
of expanHowever, recent laboratory work has shown that the degree
many
and
montmorillonite
illite,
sion and hence the basal spacings of
external
of
type
the
varying
by
be Jhanged
other 2:1 minerals .a.,
"asily
been altered'
cation. Table 1 lists some of ttt" Z t 1 minerals which have
and the retreatment
chemical
or
the original 001 spacing, the physical
external
the
treatment
proper
by
that
sulting-O01spacing. ft i. uppu.""t
the reand
K
by
replaced
be
can
cation-sin the expanded 2: i minerals
a wide
addition
In
variety'
sulting clay will be of the non-expanded'
replacby
expand
to
made
be
can
.rariety of non-expanded 2: 1 minerals
of the
case
In
the
cations'
hydrated
ing the external K by -or. highly
material
grind
the
to
only
necessary
Na based -ica, paragonite, iiis
to clay size in order for it to expand'

CHARLE.J EDWARD WEAVER

Taslr 1. Vanranoxs Paolucno rN 001 Spactwcs
Final
Original
Material

001
Spacing

inA
Nagelschmidt

9 . 7 - 1 2. 5

(re44)
Barshad

( lp material
eached with
MECL

(1e48)

Barshad

|
I

3 months

Paragonite

(1es0)

14.47

14.3

White (1950)

Soaking in MgCl,

14.O

Caillbre and
H6nin (1949)

Montmorillonite
Nontronite

Boiling in KOH
Boiling in KOH

32 hours

t0.2
10.0

Barshad

Vermiculite

Leaching rvith
KCrHrOz

10 days

10.42

(1e48)
Nortland and
Gieseking

Montmorillonite
Hectorite

(1es1)

9.90
10.09

Kunze (1952) Vermiculite

Weaverand

I Mixed la1.er

Bates
(1e51)
1

ll

I ro.o

Boiling in
KCgH:O: solution

10minutes

Wetting and drying from KOH

solution

15 times

10.0

This evidence would indicate that the 001 spacing

of the 2:r rayer
lattice silicates and therefot'e their state of expansion
is independent of
the composition of the 2:1 lattice and dependsonly
upon the type of
external cation present.
Diferential Thermal Analysis Data
An examination of the difierential thermal data shows
that the characteristic hydroxyl-endothermal reaction of illite
occurs between 500
and 650o C.; however, this figure is determined
largely from samples
obtained from the Carboniferous rocks. When illites
from totally dif_

A CLASSIFICATION OF THE 2:1 CLAY MINERALS

70r

ferent sourcesare examined it can be expectedthat this range will be extended; this is indicated by the Ballater illite described by MacKenzie,
Walker, and Hart (1949). The hydroxyl-endothermal reaction of this
material occurs at 713" C.
The majority of the montmorillonites derived from the Cretaceous
and Tertiary ash beds have a hydroxyl-endothermal reaction which is
restricted to a 650-700" C. range. Ilowever, Mg and Fe montmorillonites
from varied sourcesextend this range down to 500 and up to 800o C'
It is generally believed that the temperature of the hydroxyl-endothermal reaction is controlled largely, if not entirely, by the various
cations in the octahedral layers. As the range in temperature of this
reaction for the two clays is almost identical, it would appear that the
composition of the octahedral layers varies within the same limits.
ChemicalComposition
As is suggested by the temperatures of the hydroxyl-endothermal
reaction, the chemical analyses indicate that the octahedral layers for
illites and montmorillonites are quite similar and in many cases the
same in composition.
The composition of the tetrahedral layers in the clays of the two groups
can be indicated only by chemical analysis. Although the ranges of the
percentage of aluminum replacing silicon overlap to a considerable extent, the available analyses(largely of bentonites) indicate that many of
the montmorillonites have a very small amount of aluminum in the
tetrahedral layer, as compared to the known illites. However, this does
not mean that a 2:l lattice with little aluminum in the tetrahedral
Iayers cannot attract potassium and form a 10 A lattice. It is simply
more probable that the potassium was never available. Neither is the
converse true. For, even if there is 15 to 20 per cent replacement in the
tetrahedral layer but no potassium is available, the lattice will be expanded. This can easily be appreciated by a study of the data presented
by Ross and Hendricks (19a5).In 25 of the 82 dioctahedralmontmorillonites analyzed, nearly 15 percent or more of the silicon ions in the
tetrahedral layer are replaced by aluminum. Using a classificationbased
on the chemical composition of the impure pyrophyllite lattice these 25
clays would be referred to as illites whereas on the basis of their degree
of expansion they would be called montmorillonites. The fact that expansion is unrelated to the amount of replacement in the tetrahedral
layers is further indicated by the work of Barshad (1950) which showed
that when the Na mica, paragonite, which has approximately 25 per cent
replacement in the tetrahedral layer, is ground to less than 0.5 microns
in size it will expand.

702

CHARLESEDWARD WEAVER

Case oJ the K-bentonites

An excellent example of the similarity of expanded and non-expanded
dioctahedral 2:l clay lattices is shown by the K-bentonites (Weaver
a n d B a t e s ,1 9 5 1 ) .
An *-ray study of several samples of K-bentonite revealed that the
material is composedof randomly interstratified layers of expanded and
non-expandeddioctahedral 2 : I clay minerals (montmorillonite and illite)
in the ratio of 1 :4.
This ratio was determined by varying the extent of expansion of the
expanded layers by treating the clay with a variety of cations. When
the expanded layers were reduced to approximately t2 A by substituting
K, Na, and NHa as the external cations the resulting 001/001 value was
10.3 A. When the expanded layers were increasedto 14-15 A by treating
the clay with H and Ca the 001/001 value was increasedto 10.9 A.
When expanded to 17 A with ethylene glycol the 00I/002 value occurred
at 9.5 A. Using the curves computed by Brown and MacEwan (1950)
the ratio of. I:4 was determined.
When the mixed layer clay was alternately wetted and dried in a KOH
solution the expanded layers were reduced to nearly 10 A and the resulting 001/001 value for the clay was 10.1 A indicating rhat most of the
clay was in a non-expandedstate.
The difierential thermal curves of these mixed layer K-bentonites
contain only a single hydroxyl-endothermal peak at approximately 700o
C. (A 600" C. peak due to chlorite is sometimes present.) The presence
of this single peak indicates that the composition of the octahedral
sheets of the expanded and non-expanded layers are similar if not
identical.
The structural formula of a K-bentonite sample is:

K.rr+.roNa.orMg.os
(Alr. 6aFe.ozMg.aa)
(Al,a6Si:.ss)Oro(OH)2.

The K is probably present in the non-expanded layers, whereas the

Ca, Na and Mg are held on the expanded layers. This relationship is indicated by the fact that K forms 80/p ol the total external cations and
the r-ray data reveals that 8O/s of total clay layers are non-expanded.
This data on the mixed layer K-bentonites indicate that the compositions of the expanded and non-expanded lattices are similar, that the
amount of non-expanded layers is directly related to the amount of K
present, and that by supplying more K in the proper manner the clay
can be transposed into the non-expanded (illite) type.

A CLASSIFICATION OF THE 211 CLAY MINERALS

703

NBro Fon Nrw APPnoacs

The above discussion suggeststhat in any given impure pyrophillitetalc structure, an expanded or a non-expanded lattice is obtained depending upon the external cations attached to it. The hydroxyl-endothermal reaction occurs at a variety of temperatures, depending upon
the composition of the octahedral layers, and does not show any correlation with the c dimension.
Although throughout the complete range of impure pyrophillite-talc
compositions, either an expanded or a non-expanded lattice can be
formed und.er a variety of conditions, there appear to be compositional
poles where one type is predominant. These poles may be the result of
three factors: (1) selectedsampling in age, location, and variety of source
rock, (2) the tendency of certain cations to occur together in nature and,
(3) the Iimited stability of certain combinations of exchangeablecations
with cationic substitutions in the lattice.
It is believed that the present poles are primarily due to the first factor.

because it is based upon criteria resulting from modifying processes

acting upon the clay, rather than upon the more fundamental composition of the impure pyrophillite-talc structure which reflects more accurately the original composition of the clay and of the source material'
PnoposBr Cr..tssrrrc.q,rroN
The result of over-emphasizing the importance of the expandability
of 2-.t clays had led only to confusion which increasesgeometrically as
more information is acquired. The author believes that the idea of expandability must be made of secondary importance and all 2:1 dioctaLiiitrat and trioctahedral clays treated as one group' with a breakdown
into. varieties based on chemical composition of the impure pyrophyllitetalclattice. The terms expandedand non-expanded(or K, Ca, Mg, etc')
can be prefixed to the variety names to indicate the external cations
present. At this stage in the development of clay mineralogy it is considered best to use a classification based on hypothetical end members
that will include all 2:l clay minerals.
Table 1 shows how all dioctahedral and trioctahedral 2: 1 minerals
with varying degrees of expansion can be organized into a compact
classification.

704

CHARLES EDWARD WEAVER

Per Cent of Total Replacement in 2: 1 Lattice

Degree
of
Expansion

Ex.
Cat10ns

>75/6 in
Tetrahedral

>25 and 175/s

in Both

Tetrite

Tetoctrite

Dioctahedral I Tri.

Dioctahedral

AI

Fe

>75/s in
Octahedral
Octrite

Tri.
Mg

Expanded

Expanded &
non-expanded

Non-expan
Tesrn

1, CressrlrcltoN

oF Tr{E 2: I Cr,av MrNnnals

Primory Dioision
The main breakdown of the 2:l clay minerals is based upon the
location of the replacement in the impure pyrophyllite-talc lattice. clays
having greater than 75/6 of the total replacement (of cations of a
greater charge by cations of a lessercharge) occurrrng in the tetrahed.ral
sheets are referred to as tetrites. clays having greater than 15/6 of the
total replacement occurring in the octahedral sheet are called octrites.
clays having greater than 25/p of the total replacement occurring in
both types of sheets are called tetoctrites.
Each of these sub groups is further divided on the basis of whether
the clay is dioctahedral or trioctahedral. The dioctahedral crays are
divided into Al and Fe depending upon which is the predominant element in the octahedral sheets. The trioctahedral clays contain Mg
(zn and others are rare) as the predominant element in the octahedral
sheets.
Seconilary Diaision
The secondarydivision is based upon the nature of the external cations
and therefore the degreeof expansion. The expanded clays have Ca, Na
and Mg, etc., as the external cations. The non-expanded clays have K.
Clays having both kinds of external cations are of the mixed layer type
containing both expanded and non-expanded layers.

A CLASSIFICATION OF THE 2i1 CLAY MINERALS

705

TrnlrrNorocv
Eventually names might be given to all possible combinations of the
two divisions; however, for the present it is believed that the use of
descriptive terms will help to avoid confusion. The illiteJike minerals
are referred to as non-expanded AI 2:I clays. Where the composition is
known they can be further defined and called non-expanded Al tetrites
or KAI tetrites, and non-expanded Al tetoctrites; glauconites are nonexpanded Fe tetoctrites; trioctahedral illites are non-expanded Mg
tetoctrites. Many of the montmorillonites are expanded Al octrites or
Ca, Na, Mg., etc., AI octrites; most nontronitesare expandedFe tetrites.
Beidellites and other mixed layer minerals are classedas expanded and
non-expanded Al tetrites or tetoctrites, or, for example, as CaKAI
tetrites or tetoctrites.
CoNcr,usron
It is thought that this arbitrary breakdown on the basis of the location of the predominant replacement in the lattice, will avoid the confusion causedby trying to classify newly described minerals by comparing them with established species.From the name the general composition of the impure pyrophyllite-talc lattice and the state of expansion
can be inferred. And by making the state of expansion secondary and
independent of composition of the impure pyrophyllite-talc lattice a
more realistic approach to the origin and genesisof these clays can be
used. The composition of the 2:l lattice reflects the original source of
the clay mineral. The composition of the external cations, and degree of
expansion, reflects environment and environmental changes occurring
during and after formation of the clay. Using this classification it is
possible to apply a descriptive name which is based upon the amount of
information available rather than a general name which implies much
more than is actually known about the clay mineral.
It is realized that this classification may be incorrect and that
eventually it may be found that the total amount of excesscharge occurring in the 2: 1 lattice, or some other factor, is the controlling force
in expansion. However, it is believed that this classification is consistent
with present data and that it is a pragmatic tool that can be used as a
clarifying agent.
RrlexlNcrs
B.nnsneo, I. (1948), Vermiculite and its relation to biotite as revealed by base exchange reactions. X-ray analysis, difierential thermal curves and water content: Am. Mineral.,
33, 655-678.
B,l.nsr.lo, I. (1950), The efiect of the interlayer cations on the expansion of the mica type
crystal lattice: Am. Mineral.,35, 225-238.
Bnrlrrv,
W. F. (1944), Diagnostic criteria for clay minerals: Am. Mineral.,30,70+-713.

706

CHARLES EDWARD WEAVER

Bnowrv,G., aNo MecEwan, D. N. C. (1950),The interpretation of x-ray diagramsof soil

clays.Part II, f ow. Soil Sci., l, ffiG|\ 1949.
Clnr,iru, W., .lNn Hfml, S. (1949),Transformationof mineralsof the montmorillonite
family into 104 micas:Mincral. Mag.,38,60G612.
KuNzn, G. W. (1952),Weatheringof micasand their role in potashfixation. Ph.D. Thesis,
PennsylvaniaState College.
MAcKnNzre,R. C., Wer,rnn, C. F., Hanr, R. (1949), Ilite occurring in decomposed
granite at Bailater, Aberdeenshire
: Mineral. M ag., 28, 707-7 t4.
Montlerto, N. M., nro Grnsenwc, J. B. (1951),Influenceof the silicateion on potassium
fixation: Soil,Scienae,7f , 381-385.
Nrcerscnurnr, G. (l9M), X-ray difiraction experimentson illite and bravaisite: Mineral.
Mag.,27r 5941.
Ross, C. S., er.toHnNomcrs, S. B. (1945),Minerals of the montmorillonite group: [/. S.
Geologica,l.Suney, Pr of. P aper, 2O5-8,27-7 9.
Wnrre, J. L. (1950),Transformationof illite into montmorillonite:SoiI ScienceSoc.o! Am,
Proc.,15, 129-133.
Wn.a.vnn,C. E., mro Blrns, T. F. (1951), Mineralogy and petrology of the Ordovician
K-bentonitesand relatedlimestones:
Geol.Soc.Am., Bul'L.62,1438(Abs.).
Manuscri.ptreceiaeilOct. 13, 1952.